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Office of 1aval Research

Contract NdøOl4_75_C_~~93f

Project No. NR 356-590

Techni cal Re}~~’t.~4o. 2 ~-“— L— -~~ —.-—

‘T HE X .A KIS(A NI L I N E ) PH T H ALOC Y A N I NA T OIRON ( f l ) , HEXAK IS(ANILINE-43-.

/ PHTUALO CYANINATO IRON(II) , AND OTHER RELATED HIGHLY SELECTIVE

NMR SHIFT REAGENTS •-

by

L Clement K.,L~oy, J. Robert/looney

aod/ Malcolm ~~~~~~~ j

/ f ’ / / /

‘I / \

~j’ I / /

—

Chemistry Department 0 D CCase Western Reserve University r~~r - ~--~ ~

Cleveland , Ohio 44106 JuN 23 j9~

June 14, 1977 9>-

Reproduction in whole or in part is permi tted forany purpose of the United States Government

Approved for Public Release; Distributidn Unlimi ted

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ABSTRACT

The si gnificant properties of three good l ron (ll ) phthalccyanine

nrnr sh i ft reagents, FePc, FePc(NH2C4H9)2, and FePc(ND2C4D9)2 and

two superior shift reagents of the same type, FePc(NH2C6H5)5 and

FePc(ND2C5D5)6 are described ari d discussed. Some of the kinds of

compounds the latter two genera l ly can be expected to function with

and some of the kinds of compounds they genera l l y can be expected

not to function with are g i ven , i.e., imid azoles , py rsdines , pyr—

rot idenes , and primary ali phatic amines ; and pyrroles , seconda ry

a li phatic amines , tertiary ati phatic amines , aromatic amines , al-

cohols , ethers, and many other compounds carry ing oxygen funct i ons,

respective l y. Where they can be clearl y i dentified ,propert i es of

these compounds wh i ch are important 1-c the behavior they show to-

wa rd the reagents are alluded to. Throughout the va l ue of the

selectivity wh i ch the reagents show with both monofunctional and

polyfunctiona l compounds is emphas i zed.

Running Head Phthalocyani natoiron(II) Shift Reagents

C0

~~• I~J ! ~~~. ;

•0

~~~~~~

INTRODUCTION

Previous work has shown that a group of diamagnetic metal porphyrin

and metal phthalocyani ne complexes functi on as effective nmr shi ft reagents

(1—4). These reagents owe their ability to act solely to the ring currents

of thei r rings; the metal ions in them, iron(II), cobalt(III), ruthenium(II),

lutecium (III), silicon(IV) , and germani um(IV), all being diamagnetic.

The iron reagents of this group are of the phthalocyanine type and show , as do

apparently most or all of thes e reagents , marked selectivity in their action.

This makes these reagents attractive from a variety of standpoints .

In the present paper , work on a group of the iron reagents is described .

Special emphasis is given to FePc(NH2C6H5)6 and FePc(ND2C6D5)6 (Pc = the

phthalocyanine ligand , C32H16N8) since these reagents have been found to

possess a particularly advantageous set of properti es.

EXPERIMENTAL

Shift Reagents: FePc. The i ron(II) phthalocy anine used was purchased

(Eastman).

FePc(NH2C4H9)2 (5). In an appara tus allowi ng flask—to—flask vacuum

disti l lation, n-butylami ne (10 ml) was vacuum distilled onto FePc (1.0 g) and the

suspension thus produced was stirred for 8 hr. The resul tant was reduced

in volume by distilling off much of the excess amine (“i 8 ml), then was

mixed wi th a 1:1 benzene-pentane solution and fi l tered. The product , a

dark blue solid , was washed and vacuum dri ed (1.2 g). An nmr spectrum of

it i ndi cated it was the sought—after compound accompanied by a small amount

of ami ne.

—~—-—-—~~~—- -. —-.-- -- -—--~~~-.-,

- 2 -

The compound was also produced by the re~ction

of FePc and excess amine in ordinary apparatus , recovered by evaporation

of the excess amine , and purified by recrystallization.

FePc(ND2C4D9)2. Using the flask-to-flask technique described for

the synthesis of FePc(NH2C4H9)2, n-butyl amine-d9 (Merck) and FePc were

reacted together and the resultant product isolated. An nmr spectrum of

this product showed that its bdtyl groups had very high isotopi c purity and

that its amino groups had reasonably high i sotopi c purity.

FePc(NH 2C5H5)6 (6). Following Linstead , a mixture of FePc (1.0 g) and

aniline (12 ml) was refl uxed for 1 hr. The resul tant was filtered and

the filtrate , a deep green solution , was cooled slowl y for 12 hr. The

product , a mass of beauti ful dark-purpl e crystals , was recovered by filtra-

tion , washed , and dried (0.80 g).

FePc(ND2C6D5)6. Using the zinc—aci d technique for reducing

nitrobenzene to aniline (7), nitrobenzene -d 5 was reduced to aniline —d 5. This

was equilibrated repeatedly (4x) wi th deuterium oxide. The ani line— d7 thus

obtained and FePc were then reacted and the product was isolated using a pro-

cedure analogous to that described for FePc(NH2C6H5)6.

The reagent was also prepared from coninercial aniline-d 7 (Merck).

Shift Complex Solutions -- FePc. The technique used to prepare a solution

of the shift compl ex of a compound produced by FePc was straiqhtforward .

Fi rst the complex was synthesized and isolated by conventional means, then

a small amount of it (~ 1-5 mg) was dissolved in deuterochloroform (“i 0.5 ml),

and finally, if appropriate , the solution was filtered.

The procedures used to make up and isolate the shift complexes of N-

methylimidazole and y-picoline are typical of those used to prepare the

compl exes. FePc(NC3H3NCH3)2 (8). A mixture of FePc (0.50 q), N-methyl-

imidazole (1.0 ml) and benzene (100 ml) was refluxed for 6 hr. and filtered.

-~~~ ,- . ~~ -~~~~~~~~~~~~~~~~~~~ -- --~~.-~~~~-~~~~ . - .--

— 3 —

The fi l trate, a deep green solution , was brought to reflux , cooled slowly,

and fi l tered. The product, large rough-surfaced purple crystals , was

filtered off and washed (100 mg). It was then crushed , washed , and dried.

Anal. Calcd. for C40H28N12Fe: C, 65.58; H, 3.85; Fe, 7.62. Found: C ,

65.70; H, 4.04; Fe, 7.75. FePc(NC 5H4C143)2 (9). With the aid of an

extraction apparatus designed to permi t the extraction of a solid at the

reflux temperature of the solvent bei ng used , PcFe (200 mg) was subjected

to the action of refluxing y-pico line (10 ml) for 36 hr. The resul tant

suspension was cooled slowly and filtered . The product , purpl e crystals ,

was washed and air dried (100 mg). It was then vacuum dried. Anal.

Calcd. for C44H30N10Fe: C , 70.03; H, 3.97; Fe , 7.50. Found: C , 69.93,

70.11; H, 3.75; Fe, 7.30.

FePc(NH2C4H9)2, FePc(ND2C4D9)2, FePc(NH2C6H5)6 and FePc(ND2C6D ) 6. The

technique used to prepare a solution of the shift compl exes of a compound

produced by FePc(NH2C4H9)2,FePc(ND 2C4D9)2, FePc (r1H2C6H5)6 and FePc(ND2C6D5)6

was very simple. One or more crystals of the reagent (~ 1- 5 mg) were

dissolved in a solution of the compound (‘\I 1—5 mg) in deuterochloroform

(‘~ 0.5 ml) and , if appropriate, the resultant solution was filtered.

Instruments -- The spectrometers used were Varian HA-lOU and XL-lO0-l5

instruments . They were operated in F.T. mode.

~~~~~~~~~~ — ~~~~~~~~~~~ --~~~--- ~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .~~ .~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

— 4 -

RESULTS AN D DISCUSSION

Features of Reagents -- Each of the reagents possesses both good and badfeatures. A good feature of the simplest of them , FePc , is that it

gives spectra which are quite simple. These contain resonances from the

phthalocyani ne ring (a low fi el d AA’B13 ’ mul tipl et) and from the compound

of interest in its bound and sometimes its free form. The key resonances ,

those from the compound in its bound form, are generally wel l separated

and not overlapped wi th any free compound resonances present.

A second good feature of FePc is its commercial availability . A

third is its stability .

On the other hand , the use of this reagent does require relatively

large amounts of the compound (and of it). Further , and for many pur-

poses more important , use of it requires two sets of mani pulations.

The nondeuterated butyl reagent which functions, as is obvious , by

an exchange mechanism , is good because its use requires only a small

amount of the compound and of it , and only a single set of manipulations.

However, it does give spectra which are more compl i cated. These contain

resonances (of varying relative i ntensities) from the phthalocyanine

ring, from buty lamine in both its free and bound forms, and from the

compound of interest in its free and bound forms. The resonances from

the phthalocyanine ring , the butylamine in its hound form, and the

compound of interest in its bound form, occur in sets (because the

solution produced by the reagent contains FePc(NH2C4H9)2, FePc(NH2C4H9)

(compound), and FePc(compound )2 but usually only one signal for each

set is observed and hence the spectra , while somewhat cl uttered , are

not difficult to deal wi th .

- —i- --- - . —-—

~- -—-— -- ~~~~~ -- -,- .-~~-~~~~~- - - - - - - .

~~~

— 5 —

The deuterated reagent is similar to its nondeuterated analog

except tha t it gives spectra lacking butyl resonances (to the extent

its buty l groups are isotopica lly pure) and thus it gives less cluttered

spectra . It is , though , much more expensive than its analog.

As wi th the butyl reagents , the nondeuterated aniline reagent is

good in that only a small amount of it is needed , only a small amount of

the compound is needed , and only a sing le set of manipulations is needed .

The spectra it gives contain resonances from the phthalocyanine ri ng ,

from free aniline , and from the compound of interes t in its free and

bound forms . Accordingly, the spectra it gives are much more desirable

than those from the nondeuterated butyl reagent.

The deuterated aniline reagc~t is superior to its analog in that

it gives spectra free of phenyl resonances (to the extent its phenyl

groups are isotopically pure). Balancing this in part is the greater

effort (or alternati vely cost) associated wi th its synthesis.

Both it and its nondeuterated analog have the advantage of generally

giving spectra in which the bound compound resonances are relatively strong.

In addi tion , both are easy to handl e and store. (While it is known from

Linstead ’s work that the nondeuterated reagent loses aniline on standing

(6), the loss of anilin e by the reagents poses no practical probl em.)

As is to be expected , other similar amine reagents can he used besides

the ones just described . For example , the compl exes of isopropylamine ,

y-picoline , and neopentylamine all can be used as reagents. However, no

reagents superior to those already described have been found (the problem

wi th the isopropyl reagent is its low stability , that with the pyridine

reagent its high stability , and that with the neopentyl reagent the intensity

of the bound and free neopentyl resonances it gives).

~

~~~~~~~~~~~~~~~~ -- —-- --- — -—- . . - -

.—.-~~~~ -. ---~ . ,— - —~~ —-~~~—— -.- . .-

~~~~~~~~~~~~~~~

- 6 -

As far as is known FePc , the two butylarni ne reagents , and the two

aniline reagents all work with the same types of amines. Consideri ng this

and the various other factors, the two aniline reagents are the reagents

which , in general , can be expected to be the ones of choice.

Based on the results of a number of experiments , the behavior of these

two reagents can be projected with conf idence with certain types of hetero-

cyclic amines , with aliphati c ami nes in general , and with a romatic amines in

general . Their behavior with a number of other types of compounds such as

ethers , alcohols , etc. can also be projected wi th confidence.

Behavior of Anil ine Reagents -- Imidazoles. With imidazoles , a very important

group of heterocyclic amines , the aniline reagents in genera l can be expected

to function wel l. (Often the spectra they yiel d with amines of this type

contain a small broad extraneous resonance in the vicinity of the phtha lo—

cyani ne resonances , but this does not interfere and causes no difficulty.)

One imidazole with which both reagents have been shown to work very

nicely is , Table 1 , N-benzylimidazole. A second with which the deuterated

reagent has been shown to work is l—eth yl — 5—phenylimidazole . (The sampl e

of this compound used was the generous gift of Prof. Ray A. Olofson of the

Pennsylvania State Universi ty.)

In functioning with imidazo les the reagents clearly react with the

pyridine -like nitrogens . The stability of the bond formed can be ascribed

in part to a contribution from ~r bonding. As is to be expected the reagents

do not function wi th imidazoles hindered at N—3 . A case in point is 1 ,2—

dimethyl i mida zole, Table 1. Another is almost certainly 4(5)-phenyl -

imidazol e. -

~~~~~~~~~~~~~~~

-;

.~ ~~~~

- . . . ;. .

— 7 —

Pyridines . The reagents generally can be expected to work wel l with

pyridi nes also. A pair of pyridines wi th which the deuterated reagent is known

to work wel l is that listed in Table 2. Since isoquino line is a pyridine

wi th which FePc works, both reagents will also certain~y work with this

ami ne.

As wi th the imidazoles , part of the strength of the Fe-N bond formed

can be ascribed to u-bonding . It is to be expected ,naturally , that the

reagents will not work wi th hindered pyridines such as quinol i ne.

Pyrroles . The reagents can be expected , as a rule , to fail to function

with pyrrol es, one of the reasons for this being the lack of fully free ,

appropriately oriented electron pairs on thei r nitrogens. As indicated , the

nondeuterated reagent does not work with pyrrole , itself.

Pyrrolidines . In contrast to the case with pyrroles , the reagents

can be expected to work wel l with a variety of unhindered pyrrolidines.

One such compound wi th which the nondeuterated reagent does work is

pyrrolidine itself.

Primary aliphati c amines. It can be assumed that the reagents

will work wel l wi th most primary aliphatic amines , e.g., n-hexylamine.

That steric effects can prevent the reagents from workinq is shown by

the case of 1-adamantylamine.

Secondary aliphati c ami nes. Wi th most secondary aliphatic amines ,

because of steri c effects, it is thought that the reagents will be in—

effective. An amine of this type with which the nondeuterated reagent is

i neffective is di-sec-buty lamine . However, with secondary ami nes which

are relatively unhindered , they can be expected to be effective. As al—

ready mentioned , the nondeuterated reagent works wi th pyrro lidine , one

such amine .

.—.—--— ~~- .--—-

- 8 -

Terti ary aliphati c amines . Again because of steric effects, it is

thought that the reagents will be ineffective wi th nearly all tertiary

aliphati c amines .

Aromatic Amines . With essentially all aromatic ami nes, it is anti-

cipated that the reagents will be i neffective.

Diamines . With those diami nes wi th which they can work , the reagents

can often be expected to react predomi nantly or solely wi th just one of the

two functions. For example , wi th l—anii no—2-diethy lami noethane the deuterated

reagent reacts only wi th the primary function. Similarly with 4—amino—

methyl pyridine the deuterated reagent reacts only with the pyridyl function

(it appears that the reagents form particularly stable shift complexes with

pyridyl and imi dazole functions).

Even with diami nes wi th identical functions the reagents can often be

anticipated to interact predominantly or sometimes even essentially solely

wi th just one of the functions under favorable conditions. Thus the non-

deuterated reagent reacts essentially wi th only one of the ami no groups of

propylenediamine when the reagent to amine rati o is high , Figure 1.

(When the ratio is low the reagent reacts wi th both qroups and forms oligo-

meric species.) Other diamines with whi ch one or the other of the two

reagents react sel ectively are ethyl enediamine , hexamethylenediamine .

and octamethylenediam ine , Table 2.

Isomeri c ami nes . Where one of a pair of isomeric ami nes bel onging to

one of the classes with which the reagents will react is hindered and the

other is not, the reagents can be expected to work selectively. For example ,

the reagents can be expected to function with 1 ,5—substi tuted imidazoles but

- ... —~~ -- —- ~~~~~~—.

— 9 —

not wi th thei r 1 ,4 i somers (the fact that the reagents can be expected to

act thus and accordingly can be expected to allow the differentiation of

1,4 and 1 ,5 imi dazole isomer pairs is of some importance because the dis-

ti nction of such pairs by ord i nary techniques is difficult (]~)) .Other Compounds. With compounds carrying many common oxygen functions

it can be anticipated that the reaqents will not work . Evidence for this

is seen in the data on the oxygen conta i ni ng compounds presented in Table 2.

Two less common kinds of compounds they may on occasion function with ,

based on Balch ’s, (8), Taube ’s (11) and Stynes ’(12) work , are isonitriles

and ni troso aromatics.

CONCL USIONS

The aniline reagents are the best of the iron phthalocyanine shift

reagents for most purposes. They can be expected to interact with certain

types of amines and not with others nor wi th a variety of common nonamine

bases and hence to act highly sel ectively both wi th monofunctional and

polyfunctional amines . They can be expected in genera l to give complexesof specifi c stoichiometry , two ami nes to one iron phthalocyanine , and

speci fic geometry , trans , and hence to yield spectra with predi ctable

and easily understandable shifts . In practice they are easy to make ,

simple to store, and uncomplicated to use.

Acknowl edgment

This work was supported in part by the Office of Naval Research.

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ . -- --~~~~~ _

—~ ——~

-. ~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~ . ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ . —

~~~~~~~~~.--

- 10 -

TABLE 1

SIMPLE AMINE S WITH ANILINE REAGENTS

Type Amine Reagent Applicabi lity~-

imidazole NCH / ~ D,H F/ 2 —

r1f l25 0 F

Cl’

H N

1HN>~

H N

C6H5

pyrrol e HN~~~ H N

pyrrolidine ~~~~ H F

prima ry NH2(CH2)5CH3 H F

H N

secondary NH(CHCH3C2H5)2 H N

~- F = fu llyapplicable; N not applicable

~~~~l_. ~~~~~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~ —~~~~ - —-—.-~~ --- -- --— .-- --- — ---- - .— --.----

-—~ —- —— ..- ~~~~~~~~~~— -~~~—.. -.~~~~~~~~~ -—-~~~~~~~~~~~~~~ —-.--

— 11 —

TABLE 2

POLY FUNCTIONAL COMPOUNDS WITH ANIL INE REAGENTS

a Act iveFunctions Compound Reagent Sel ectivi ty— Funct ions

-NH2 ~ N3CH2NH 2 0 F

EN -NH2 H2CH2CH 2N(CH 2CH3)2 0 F NH 2

—N H 2 — NH 2 NH 2 (CH 2 ) 2 NH 2 H P both NH 2

NH 2 (CH 2 ) 3NH 2 H P both NH 2 INH 2 (C112 )6 NH2 D P both NH 2 1NH2(CH 2)8NH2 H P both NH2 11

~C=O ~N N~~CCH3 D F ) I

N3CH 0 F )-OH -NH2 NH2(CH2)60H 0 F NH2

-OH -0- -NH2 NH2(CH2)3(OCH2CH2)20H D F NH2

F = fully selective; P partially selective

L , ., ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ . . _ _ _

_ _ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ . . - —

I,

r— 1 2 —

REFERENCE S

1. J. E. Maskasky and M. E. Kenney, J. Amer. Chem. Soc., 93, 2060 (1971).

2. J. E. Maskasky, J. R. Mooney , and M. E. Kenney , J. Amer. Chem. Soc.,94, 2132 (1972).

3. M. Gouedard , F. Gaudemer , and A. (~audemer , Tetrahedro n Lett., 25, 2257 (1973).

4. W. deW . Horrocks , Jr. and C. Wong, J. Amer. Chem . Soc., 98, 7157 (1976).

5. B. W. Dale , R. J. P. Williams , P. R. Edwards , and C. E. Johnson ,Trans. Faraday Soc., 64, 620 (1968).

6. P. A. Barrett , D. A. Frye, and R. P. Linstead , J. Chem. Soc., 1157 (1938).

7. L. F. Fieser , “Organic Experiments ,” pp. 181—184 , Ratheon Education Co.,Lex ington, Mass., 1968.

8. J. J. Watkins and A. L. Blach , Inorg. Chem., 14, 2720 (1975).

9. A. Hudson and H. J. Whitfi eld , Inorg. Chem., 6, 1120 (1967).

10. H. R. Matthews and H. Rapoport , J. Amer. Chem . Soc., 95, 2297 (1973).

11 . R. Taube , Pure App l . Chem ., 38, 427 (1974).

12. 0. V. Stynes , J. Amer. Chem . Soc., 96, 5942 (1974).

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17. D ISTRIBUT ION S T A T E M E N T (of the ab,t rsct enter ed in Block 20. if different Iron, !~rport)

1 9. S U P P L E M E N T A R Y NOTES

¶ 9. KEY WOR DS (Continue on rev er s e side if necessary and iden Iffy by block number)

Nuclear Magnetic Resonance Spectroscopy , Shift Reacents , Phthalocyanines ,Iron, Amines

20. A~~S1RA CT (Cont inue on rsver~ o aid. If nece ss a ry and identify by block number)

The significant properties of three good iron(II) phthalocyanine nnir shiftreagents , FePc , FePc ( NH2C~H9)2, and FePc(ND2ChD9)2 ~nd two superior shift re-agents of the same type, FePc(NH 2C6H5)6 and FePc (N02C6D5)6 are described anddiscussed . Some of the kinds of compounds the latter two generally can be ex-pected to function with and some of the kinds of compounds they qenerally canbe expected not to function wi th are given , i.e., imi dazo les , pyridines , pyr-rol idenes , and primary ali pha ti c ami nes; and pyrroles , seconday aliphati c

DD 1 JAN 73 1473 EO IT IO N OF 1 N0V 65 IS O B S O L ET E

S E C U R I T Y C L A S S I F I C A T i O N OF T H I S PAG E (l4 o l ’a r . F n t e r e d )

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SECURITY C L A S S I F I C A T I O N OF THIS PAGE(iTh.n Data Eni.r.d)

20. (cont.,) amines , tertiary aliphati c amines , aromati c amines , alcohol sethers, and many other compounds carryi ng oxygen functions , respectively.Where they can be cl early identifi ed, properties of these compounds which reimportant to the behavior they show toward the reagents are alluded to.Throughout the value of the selectivity which the reagents show with bothmonofunctional and polyfunctiona l compounds is emphasized .

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